Azo dyestuffs



United States Patent "i 2311654 Patented Dec. 24, 1957 aminoazo compound or one mol of an amino compound 2,817,654 of any other composition and which is capable of con- AZO DYESTUFFS Ipiling, are condensed with one mol of a dicarboxylic acid alide of the formula Philippe Grandjean, Markus Kappeler, Lukas Schneider,

and Willy Steinemann, Basel, and Walter Wehrli, 5 Hal-COCx=CH--CO-Hal (II) Riehen, Switzerland, assignors, by mesne assignments, to $aul & Co., Newark, N. J., as nominee of Fidelity wherein Hal stands for chlorine or bromine, and x stands nmn T ust C mpa y, executive ust un and for hydrogen, chlorine, bromine or methyl. Thereafter, Trust if necessary and, if desired, after preliminary coupling No Drawing Application June 15, 1953 with a suitable diazo compound, the obtained disazo or Serial 361,329 polyazo dyestutr is treated in substance or on the fiber with a metal-yielding agent.

A further embodiment of process according to which a series of disazo and polyazo dyestuffs of the present invention can be prepared, involves coupling one mol of a The present invention relates to valuable disazo and dipyl'alolone 0f the formula Claims priority, application Switzerland June 16, 1952 6 Claims. (Cl. 260-147) HC--C-OH: aC-CGH HO N IL iioH N- CH=CHONHC 0C2:=CHO O-NH-C C H=CHON S OaH SOxH oal! 40:13: (111) polyazo dyestuffs and to the preparation thereof, wherein x has the previouslyrecited significance, with two In accordance with the present invention two mols of an mols of the diazo compound of an amine of the benzene aminoazo compound of the formula or naphthalene series, other than l-aminobenzene-Z-carboxylic acid or l-amino-4-sulfobenzene--2-carboxylic acid or 1-am1no-5-sulfobenzene-Z-carboxylic acid, which H0- amine may be substituted in ortho-position to the amino N GH=CH NH, group by a group which is capable of metal complex formation and which may also hear additional substitu- SO|H $0111 (I) ents including arylazo substituents, or simultaneously or wherein R stands for a radical of the benzene or naphthaany desired 936611161196 with two mols 9 two mutually lene series, other than the ortho-carboxybenzene, orthodlfiel'Fnt Such 11am componPnts of Whlch one may be carboxybenzene-Ineta-sulfonic acid and ortho-carboxybenflla dlaz? component of 1'ammobenzePez'Farboxylic f zene-para-sulfonic acid radicals, and wherein the R radical 40 or 1'ammo'4'sulfobenzenfi'z'cafrboxyhc acld or f may contain in m-tho position to the a group S-sulfobenzene-Z-carboxyl1c acld, and thereafter treating which is capable f metal Complex f ti and may the obtained dlsazo or polyazo dyestufl? 1n substance or on also contain additional substituents including arylazo subthe fiber with a metal-Yielding agentstituents, or two mols of the corresponding metallized The new dyestuffs 0f the P1765511t invention, in the metalaminoazo compound, or two mols of a mixture of two free state, correspond to the formula:

R-azo'C COH: no-- it N CH=CH NH-CO-Cz=Cz-C0A' 02H BOIH (IV) such aminoazo compounds, in one of which R may be the wherein R has the hereinbefore-recited significance, one ortho carboxybenzene, ortho-carboxybenzenemeta-sul- 2: represents hydrogen, chlorine, bromine, or methyl, fonic acid or ortho-carboxybenzene-para-sulfonic acid while the other z stands for hydrogen, and A stands for radical, or a mixture of one mol of such aminoazo coma moiety of the formula A, wherein R may also represent pound (I), wherein R has the initially-recited significance, the ortho-carboxybenzene or ortho-carboxyben2ene-metabut including the ortho-carboxybenzene, ortho-carboxysulfonic acid or ortho-carboxybenzene-para-sulfonic acid benzene-meta-sulfonic acid or ortho-carboxybenzeneradical, or the radical of an aminoazo compound of any para-sulfonic acid radical, with one mol of any other other desired composition.

(Eoupling of the aminoazo compounds or of the amino compounds which are capable of coupling, takes place according to the first embodiment of the process of this invention, with the aid of an unsaturated dicarboxylic acid halide of Formula II. Such halides comprise inter alia the dichlorides and dibromides of fumaric acid, maleic acid, methyl-fumaric acid, methyl-maleic acid, chloro-fumaric acid and bromo-fumaric acid. Possible losses due to hydrolysis may be compensated for, if necessary, by using the dicarboxylic acid halide in slight excess. I

In carrying out the process, the aminoazo compounds or the amino compounds which are capable of coupling, are dissolved in water and, preferably at low temperature (about to about 30), are admixed with the dicarboxylic acid halide (II). The mixture is stirred vigorously, care being taken to constantly neutralize liberated hydrogen halide, by the addition of acid-binding agents, such for example as sodium bicarbonate, sodium carbonate, sodium hydroxide, or corresponding lithium or potassium compounds, or alkaline earth metal oxides or carbonates, or suitable tertiary organic amines. The dicarboxylic acid halides can, if desired, be diluted by an inert solvent, such for example as benzene, methylbenzene, chlorobenzene, carbontetrachloride or chloroform. The condensation is completed when free amino groups are no longer detectable, the reaction product may partly or wholly separate out during the reaction with the acid chloride, or it may be isolated from the reaction solution by salting out or by acidification. After being filtered off, it is washed, if necessary, and finally dried.

A homogeneous dyestuif, which is symmetrical in respect of the interconnected amines, is obtained when two mols of the same aminoazo compound (I) are bound together with the aid of one mol of dicarboxylic acid halide (II). When on the other hand, two mols of a mixture of two different aminoazo compounds or a mixture of an aminoazo compound and an amino compound which is capable of coupling, are involved in the condensation, there is obtained a mixture of one asymmetrical and two symmetrical dicarboxylic acid derivatives. The mixture contains as predominating constituent a component of the formula i f '-z (v) wherein x stands for one and z'- stands for the other aminoazo compound which is acylated inthe amino group orv for one and; the other amino compound capable of coupling, respectively, and y" stands for the radical of the dicarboxylic acid corresponding to thedicarboxylic acid halide (II). There are also present the two products of the formulae The two mutually different aminoazo compounds or the aminoazo compound and amino compound which is capable of coupling, a total of two mols in each case, may be bound together in the proportion 1:1 with one mol of dicarboxylic acid halide (II). However, other mixture proportions such for example as 4:1, 3:1, 2:1, 1:2, 1:3- and 1:4 also yield valuable dyestuffs, including some which are characterized by properties superior to those wherein the mixture proportion is 1:1.

Where the disazo or polyazo dyestuff is built up from an aminoazo compound (I) and an amino compound which is capable of coupling, it can easily be converted into a dyestutf mixture of; Formula IV by coupling with a suit-, able diazo compound.

The dipyrazolone of Formula III, employed in the second; process embodiment of the invention, may be. prepared, for example, by reacting one mol of a, dicarboxlyic acid halide of Formula, II with twomols, of 4-amino-. 4'-nitrostilbene-2,2'-disulfonic acid, converting the ref.

sultant dinitro compound into the corresponding diamino compound and then into the dihydrazino compound, and condensing the latter with an acetoacetic acid alkyl ester. The coupling of the dipyrazolone with the diazo compounds is carried out in aqueous medium, if desired in the presence of organic bases such for example as pyridine and its homologues. The reaction may take place in molecular proportion, provided that there are two mols of diazo compounds per mol of dipyrazolone (III). The two mols of diazo compounds may be constituted by a single compound or by a mixture of two different diazo compounds. In this case also, it is possible to modify the products of the final dyestufi to some extent as desired by changing the proportion of the two different diazo compounds from 1:1 to for example 4:1, 3:1, 2:1, 1:2, 1:3 or 1:4, provided that in each case a total of two mols of mixture of diazo compounds participate in the reaction for each mol of dipyrazolone (III).

In view of the manifold possibilities with respect to the construction thereof, the new dyestufis may possess almost any desired shade. They dye cotton and fibers of regenerated cellulose, some in the single bath or aftermetallizing processes, in shades which are of very good fastness to light and of excellent Wet-fastness and many of which are of surprising purity.

The disazo and polyazo dyestuffs can also, in part, be converted in substance into the corresponding metal complex compounds by treatment with metal-yielding (e. g. Cu, Ni) agents. Coppering, for example, may advantageously be carried out, where one of the groups to be metallized is an alkoxy group, under conditions whereby a dealkylating splitting of the alkoxy group takes place. This can be, Carried out according to methods per se known from the literature, for example by heating with a copper salt in a weakly acid to weakly alkaline aqueous medium, if desired with the use of pressure and/or in the presence of ammonia or organic bases, or it may be carried out in a melt of alkali salts of low molecular aliphatic monocarboxylic acids.

The preparation of disazo and polyazo dyestuffs, metallized in substance, according to the first embodiment of the process, can also be carried out by interconnecting the aminoazo compounds in the form of their metal complex compounds with the dicarboxylic acid. halide (II). Where dyestufis mixtures are being prepared, the two aminoazo components may be singly or simultaneously subjected to metallization and then to condensation with the dicarboxylic acidhalide.

The disazo and polyazo dyestuffs, metallized in substances, also dye cotton and fibers of regenerated cellulose in. a wide; variety of shades, many of which are of high purity and: all of which, are characterized by very good fastness tolight and by excellent wet-fastness properties.

The above. described: dyestuffs, in like composition, can alsobeprepared by. admixing the individual non-metallized and/or metallized disazo and/or polyazo dyestuffs, the resultant mixtures being in many cases at least equivalent to the hereinbefore-described mixtures, obtained during themanufacture of the dyestuffs.

The following examples set forth represent illustrative embodiments of the invention. In these examples, parts and percentages are by weight, and temperatures are in degrees centigrade.

EXAMPLE 1 26.8 parts of the aminodisaz'o dyestutf correspondingto the formula (VIII).

I 2,817,654 6 and 30.0 parts of the aminomonoazo dyestufi correspond- The isolated dyestutf mixture, which is a brown powing to the formula I der, dyes cotton and fibres-of regenerated cellulose in i yellow-orange shades, the fastness properties of which H.c- |J--'-C-N=N can be improved by aftertreatment with copper-yielding OH 5 agents- H H 000E Dyestulfs of similar properties are obtained when, in N the foregoing, the radical (1) of the first of the enumer SOH SOH (Ix) ated reaction components is replaced by another amine of the benzene series which is capable of coupling as for a dISSOlVBd In Water at room temperature h the example by the radical of 1-amino-2,5-dimethylbenzene dition of aqueous sodium hydroxide solution. Into the or f 1 i -2 h 5. h lb f1..a ino resultant solution, there are simultaneously added drop- 3- 1 j b wise and while stirring thoroughly, on the one hand a mixture of 7.7 parts of fumaric acid dichloride and 8 EXAMPLE2 parts of benzene and, on the other hand the requisite amount of aqueous sodium carbonate solution to main- 33.3 parts (0.033 mol) of the copper complex comtain the reaction of the condensation solution weakly pound corresponding to the formula alkaline throughout. After all the fumaric acid dichloand 49.5 parts (0.067 mol) of the copper complex of the ride has been added, stirring of the condensation soluaminoazo compound corresponding to the formula HOlS- COOK H0C\ I SOaH 503E (XI) tion is continued until free amino groups can no longer are together dissolved in water with the addition of aquebe detected. The resultant disazo dyestufi mixture, the ous sodium hydroxide solution, and then condensed after unsymmetrical component of which corresponds to the the manner described in Example 1 with 7.7 parts (0.05 formula mol) of fumaric acid dichloride. The isolated dyestufi 'on door! slain son:

01H is then precipitated from the warm condensation solution with the aid of sodium chloride, after which the precipimixture, the unsymmetrical component of which corretate is filtered OE and dried. sponds to the formula V $817,351 "7 us is a dark powdet which dyes cotton and fibers of regenarenobteinedlwhen, in the first' of the enumerated reacerated cellulose in pretty green shade of good fastness tion components, on the one hand the B-aminopyrenedi to light, Sulfonic acid is replaced by an aminonaphthalene-disul- Dyestuffs with similar properties are obtained when i fonic acidsuc'h for example as 2-aminonaphthalene-4,8- the first-mentioned reaction component, the LS-dihydisulfonie acido'r 2-am'inonaphthalene-6,8-disulfonic acid droxynaphthalene-3,d-disulfonic acid moiety is replaced and/or .on the other-hand the l-amino-fi-methylbenzene by the. 1-hydroxynaphthalene-4-sulfonic acid moiety or is replaced by another amine of the benzene series'such by the 2-hydroxynaphthalene-4-sulfonic acid moiety or forexample as aminobenzene, l-amino-Z-methylbenzene, by the 2-hydroxynaphthalene-6-sulfonic acid moiety or I-ahaino-3-ethylbenzene, 1-amino-2,S-dimethylbenzene, 1- by the 2-hydroxynaphthalene-6,8-disulfonic acid moiety, 1.0 amino-2,5 diethoxybenzene, l-am'ino-B-acetylaminoben and/or the lamigoa8-hydroig naphthalengfi,g-disulfonlic zene or 1 amino-2-rnethoxy-5-rriethylbenzene. acid moiety is rep need by t e l-aminoy roxynap tha1ene-4-sulfonic acid moiety. EXAMPLE 5 34 parts' of aminoazo compound corresponding to For- E M 3 5 mula'XI and 309- parts of the amino azo compound corresponding to the formula 24.7 parts of the am noazo compound obtained by M coupling diazotized 1-amino-3-carboxy-4-hydroxybenzene- 5-sulfonic acid with 1-amino-3-acetylaminobenzene, and

30 parts oi the aminoazo compound corresponding to Ho:s N Formula IX are dissolved in water with the addition of I NH sodium hydroxide and condensed after the manner de- O scribed in Example 1 with 7.7 parts of fumaric acid di- I chloride. The isolated dyestuff mixture, the unsymmetriare dissolved in 2000 parts of water containing sodium cal component of which corresponds to the formula hydroxide and adjusted to a pH of about 8. After the COOH [03K SOsH is a brown powder; it dyes cotton and fibers of regensolution has been cooled to 5-8 by the addition of ice, erated cellulose in yellow shades, the fastness properties there g thtireto at the s temperature, in the of which are im roved b aftertreatment with co eryielding agents. p y Pp course of 1 to 2 hours and while stirring very thoroughly,

Dyestuffs with similar properties are obtained wh a 20% solution of fumaric acid dichloride in chloroifl e fi e 0f the aforementioned reaction pf fa 40 benzene, until free amino groups are no longer detectable.

the 1-am1no-3-carboxy-4-hydroxybenzene-5-sulfon1c acid Durin this 0 e th 1 is replaced by. 1-(4-amino)-benzoy1amino-3-carboxy-4- P fa reac so u Ion 1S constantly hydroxybenzene-S sulfonic acid and/ or the l-amino-B- mamtamed Weakly alkaline (P of about y the p acetylaminobenzen? is replaced y 0 0f the Other amines Wise addition of dilute-aqueous sodiumhydroxide solution.

of the benzene'isenees. numer'ated m Example v v p The reaction solution is then heated .to 80 and the re- EXAMPLE 4 mnanrfiiiinurm isazo dyestuffs is salted out with so- 24.8 parts of the aminoazo compound obtained by coudiumchloride and isolated by filtration.

pling diazotized S-aminopyrenedisulfonic acid with 1- In de amino-3-methylbenzene, and 37 parts of the copper comor r to convert the product Into the copper plex of the aminoazo Compound Corresponding to FOP plex compound, it is dissolved in 1000 parts of water at mula XI are dissolve-d in water with the addition of aque- After the addition of 15 Parts of Sodium acetate 0118 sodiumhydl'oxlde solutlofl, after Whlch condensatlon to the resultant solution, there is added to the latter, in

is carried out after the manner described in Example 1 with 7.7 parts of fumaric acid dichloride. The isolated 55 the course of about 30 mlnutes and while P thor' dyestufi mixture, the unsymmetrical component of which oughly a 2 3411939115 PP sultatelsohltloh until copper eorre pondstoithe formula ions; can 'be' detected in, a salted; out test specimen.

SOZH

H3CC C'-N=N 1 CH. II N\ /OOCuOfiI SOIH no. N=N NHCO-CH=CH-CO-NH OH=CH -N I A0811. S OaH is a yellow brown powder which dyes cotton and fibers. Tho copper comp lexicompound isthemisolated, dried of regenerated cellulose in reddish yellow shades of very; and ground. The unsymmetrical component thereof corgood fastness to light. Dyestuffs of similar properties .15 ,responds--to the formula i I HOaS- t Jo-ou-oc HaG-W-( N=;N

N oo-oh-oo sons NH-COOH=CH-GONH N and is a brown powder which dissolves with yellow coloraare dissolved in 2200 parts of water with the addition of s Water and 111 collllcemratded sulfllllnc f -d i the necessary quantity of lithium carbonate to achieve yemgs on cotton are ye ow an are c aracterize y 1 excellent fastness to light and to wet treatmentscomplete dissolution. After cooling the resultant soiu A similar dyestuif which is also characterized by extion (P about by the addition there .cellent fastness properties is obtained when the aminoazo is added dropwise in the course of 1 to 2 hours and while compoulld (XII) of i preseni example is replaced by stirring thoroughly, a 10% solution of fumaric acid dithe equivalent quantity of ammoazo compound corresponding to the formula chloride in methylbenzene until free amino groups are no longer detectable. During this operation, the reaction Hoss- N=N* C C CH' solution is maintained weakly alkaline (pH=8.0) 000E throughout by the suitable addition of a small amount of sodium carbonate. The reaction mixture is heated to 80- (XHD 90 and the dyestufi isolated after the manner of the pre- EXAMPLE 6 vious examples. The unsymmetrical component thereof 30 parts of the aminoazo compound corresponding to corresponds to the formula 00 OH HO H in N=N-E 11-0 0NH-- NH-CO--CH=CHCONH- 00011 3 0311 the formula in the dry state, it is a, yellow powder which dissolves with yellow coloration in water and in concentrated sulfuric N=NC-CCH: acid. It dyes cotton and fibers of regenerated cellulose in clear yellow shades which, particularly when they are COOH 110-0 N treated with copper-yielding agents, are very fast to light \NLQQH=CHQNH' and to wet treatments.

03H sour EXAMPLE 7 and 21 parts of the aminoazo compound corresponding Parts of the ammoaZO compound Whlch coll'espmlds to the formula to the l' l in approximately 2 hours and while stirring thoroughly,

0 OH HO-(L 112 EXAMPLE 8 34 parts of the aminoazo compound corresponding to the formula 803B 80:]?! (XVII) are, in the form of the trisodium salt thereof, dissolved in a 20% solution of symmetrical maleic acid dichloridejn 1800 parts of water, and then condensed with fumaric benzene is added until the reaction solution contains no more free amino groups. Ihereuponthe reaction soludyestuffs is isolated.

acid chloride after the manner described in Example 5. The resultant disazo dyestuff is isolated and converted into the copper complex compound thereof, after the manner hereinbeforedescribed. The product corresponds to the In order to convert the same into the copper complex formula compound, the method described in Example 5 is carried out.

The isolated, dried and ground copper complex compound, the unsymmetrical component of which corre- 35 sponds to the formula OCH:

and is a brown powder which dissolves with yellow coloration in water and in concentrated sulfuric acid, and dyes cotton and fibers of regenerated cellulose in pure yellow shades with excellent fastness to light and wet treatments. In order to convert the disazo dyestutf into the nickel N o o-oh-o ("3- sonar SOIH complex compound, parts of the disazo dyestulf are dissolved in 1000 parts of water. 15 parts of crystalline sodium acetate are added to the solution, followed by the addition, at about 70 C. and in the course of 20 to minutes of a 10% aqueous nickel sulfate solution until a permanent excess of nickel (II) ions can be detected. The resultant nickel complex compound is precipitated from the solution by the addition of sodium chloride, after which it is filtered off and dried. The product dyes cotton and fibers of regenerated cellulose in yellow shades of good fastness to light and to wet treatments.

EXAMPLE? =0 12 17 parts or the aminoazo compound corresponding to 9 the formula Hots- N=N- J- :-cm Ho-d l v N OCH=CH NH:

13 are dissolved in 500 parts of water with the addition of sodium carbonate, and are then subjected to condensation with fumaric acid dichloride after the manner described in Example 5. The thus produced disazo dyestufi is separated and dried. It corresponds to the formula SOaH EXAMPLE 10 15.4 parts of the aminodisazo compound corresponding to the formula Hacare in the form of the copper complex compound, dissolved in 500 parts of water with addition of sodium carbonate, after Which condensation is carried out with fu- "maric aciddichloride at 10 to 20 in the manner described in Example -5. The thus-produced tetrakisazo dyestuif which corresponds to the formula "14 is a black powder which dissolves with blue-violet colora;-- tion in concentrated sulfuric acid and dyes cotton and fibers of regenerated cellulose in brown-violet shades of good fastness properties. U

The same dyestutf is obtained when 2 mols of the diazo compound of 4-amino-2-methyl-5 methoxy-l,1'-azobenzene-4'-sulfonic acid are coupled with 1 mol of the dipyrazolone corresponding to the formula \NZOCEBCHGNEPO 0-011: 1

SOsH 803E 2 and the resultant tetrakisazo dyestufi subjected to demethylating coppering.

EXAMPLE 11 14.9 parts of the aminoazo compound which corre- CH=CH NH;

BOsH (XIX) sponds to the formula N WH NH.

are, in the form of the copper complex compound, dissovled in 300 parts of water with the addition of lithium carbonate and then condensed with fumaric acid di- 7,654 [To chloride aft th mann he e nbe o e descr h a p The c pp plex compound t ereof, as thus obtained .d sazotdyestufi co esponds to the form w l a its ni kel complex comp und, dye cotton and HOaS N-;N-(|3i|J-om I --oi1-o o /N SOaH S0311 v 2 and is va dark brown powder which dissolves with yellowfibers of regenerated cellulose in yellow shades which are ish red coloration in water and in concentrated sulfuric fast to light and to washing. The same dyestuffs are obacid, and dyes cotton and fibers of regenerated cellulose tained when the 34 parts of the aminoazo compound in brownish red shades of good fastness properties. (XVIII) are first converted into the corperdwrhthe nickielll) comp ex compound, and then com ine t rough e EXAMPLE 12 medium of fumaric acid dichloride, with 1-[4"-amino- 76:3 parts of the aminodisazo compound which correstilbenyl (4')] 3 methyl 5 pyrazolone 2',2 disponds to the formula sulfonic acid, and the resultant intermediate further 1.00M. 000B .10.! l

H006 N CH=CH NH.

| S OaH SOaH (XXII) are dissolved in water with the addition of lithium carbonworked up as previously described. A dyestuff with ate, and are then condensed with fumaric acid dichloride similar properties is obtained when the 11.5 parts of 1- in the manner described in Example 1. The resultant amino-2-carboxybenzene-4-sulfonic acid methylamide tetrakisazo dyestuff is salted out at the boil, and is then are replaced by 10.9 parts of 1-amino-2-carboxybenzenefiltered off and dried. It corresponds to the formula 4-sulfonic acid. The nickel complex compound, obtained SOaH $0311 2 and is a red-brown powder which dissolves with red by warming the dyestuff with nickel sulfate in the prescoloration in Water and in concentrated sulfuric acid ence of sodium acetate, dyes cotton and fibers of regenand dyes cotton and fibers of regenerated cellulose by 'erated cellulose in fast yellow shades.

the after-coppering process in brown-red shades of good In the following table, additional dyestuffs are set forth fastness properties. which are prepared after the manner set forth in Ex- EXAMPLE 13 amples 1-13. In this connection the fumaric acid dichloride or furnaric acid dibromide can be replaced by 4P th IQ Q Q ompo I an 2 6 symmetrical maleic acid dichloride or methyl-furnaric Parts of y )l y -py e5 acid dichloride or dibromide or methylmaleic acid dilone 2',2"-disulfonic acid are dissolved in 1500 parts of chloride or dibromide or chloroor bromo-fumaric acid Water With the additiOIl f illI l nate a d h n dichloride or dibromide. In all cases similar valuable condensed with 7.7 parts of fumaric acid dichloride azo dyestuffs are obtained.

after the manner described in Example 1. The resultant In most cases, sodium hydroxide or sodium carbonate mixture is cooled to 0-5 and the diazo suspension from is employed as acid-binding agent; however, this agent 11.5 parts of 1-amino 2-carboxybenzene-4-sulfonic acid may with similar success be replaced by lithium carbonmethylarnide added thereto. Upon completion of the ate, sodium or potassium acetate or bicarbonate, potascoupling, the resultant unitary di sazo dyestufi? is saltedsium hydroxide or carbonate, calcium hydroxide or carout at about 90, and is then filtered off and dried. It bonate, magnesium oxide or N,N-dimethylaminobenis identical with the product obtained according to Exzene,

. EH59 ou 23 smc ww m onwuugfigdwhuohuhaiflugfio n 8a+o E2E84 S #6 l l 2.. 2 OQNNV 2 a .l 6 EE: kemwm uammhu M5523 8: 3 o ozsm nqwN553?; hufiuhn *MS E Z QQ e E fiSm E n EE G 5 3 SHENHV 3 H n nwn 5 quenfioo 3358 R500 I l .l. 12.-..-. 2 Q iZ5m d 5 2 H1O N-Om mz A v mo m o UZ MW nm om m0 EO O C H H d omaflo o 1. 05 2 0E ed 1. an n A v Q a l v $233 m5 New F2 WO ND Z -=M 03 NO mo o o z z v a E5 323 dv- 23 2:8?2655&6? $5. 27; hua ae w fiw s 532 E v .1. EEMNV 2 a i. m n 8 l 4553 E 8 E2 flan e E5528 .534 33 o ou m unouagsu muonuma $59.5? 58 55253a& 85 H 2 L. 2.. aud 3 A 8 How EU ES komneh 3. Q O 35 e GHQ B 5388 258 208 v B2 53 ww hfiw e 523 5680 E a fi a 5 3 9530 3 6 95358 M0358." 9.0 I. hno wafl 595a? A V B 1 hno wiflB 5338 Ag NV SE n m 3 5 81" a F ha" 223% 5 0 B ESQQ QE 523B Q O 38 a B fi ufi fi 2 -21 5 KB 5 3 2530 88 H Ei s 5 5630 3 A8 5 A8 5 3 do M QD o 83% 3 8 vnucnfioo $5584 388m 353500 28534 2a 295* 2: S 7 aw 3 am mica-cause 38595 a 3:5 a 8:? 838.5% .8 @3832 E3 2.353 H0 88 0 dcflnmnwudog Representative examples are Examples 317 and 45. The dyestulfs according thereto" correspond to the formulae:

EXAMPLE 37 SOaH Mina...

sol-Nn-om EXAMPLE 45 as by 43.4 parts of 1anihio z carboxybenzene csulfonic acid amide or a mixture of 23 pans of l ainino-2-carboxybenzene-4-'sulfonic acid methylamideand 21.7 parts NH-C O SOrH SOsH NGCHHOWLO N of 1-amino-2-carboxybenzene-4-snlfonic acid or a' mixture of 21.6 parts of 1-amin0-2-carboxybenzene-4-sulfonic acid amide and 13.7 parts of 1-aminobenzene-2 carboxylic acid.

NQCH=CHQNH(!JO EXAMPLE 52 CH 8083 S0811 g The diazo compound of 18.8 parts of l-hydro'xy-Z- 1 aminobenzene-4-sulfonic acid amide is coupled with 49.1 NH-CO parts of the dipyrazolone (XX) in a solution which is rendered slightly alkaline by means of sodium carbonate. O Upon completion of the coupling which can [be accelerated by the addition of pyridine, the disazo dyestutf is sepa- Q9Q 39 x rated and dried. It corresponds to the formula H|NO:S- N=NC-G-GHa OH HO'O\ NO6HCHONHCO-CH= SOaH SIOIIH ..|2 EXAMPLE 51 and is a brown powder which dissolves with yellow 46 parts of 1-=amino:2-carbexybenzenen smfonie acid methylamide are diazotized and coupled in solution which is alkaline with sodium carbonate, with 98.2 parts of the dipyrazolone corresponding to Formula XX. Upon completion of the coupling the reaction mass is warmed, a small quantity of sodium chloride added and the mixture boiled until the dyestuff pul is converted into a readily filtrable precipitate. This precipitate is filtered ofi hot, and is then dried. The thus-obtained disazo dyestufi is identical with the product obtained according to Examples 8 and 13. In order toconvert the disazo dyestuff into the nickel complex compound, 50 parts of the disazo dyestufi? are dissolved in 2000 parts of water. 30 parts of crystalline sodium acetate are added to the solution, after which there is added, at about 70 and in the course of 20-30 minutes, enough of a 10% aqueous nickel sulfate solution so that a permanent excess of nickel (II) ions are detectable. The resultant nickel complex compound is precipitated-from thesolution by the addition of sodium chloride and is then filtered off and dried. It dyes cotton and fibers of regenerated cellulose in yellow shades of good fastness to light and to wet treatments. Similar dyestuffs are obtained when, on the one hand the fumaryl bridge of the dipyrazolon' (XX) is replaced by the methylfumaryl bridge coloration in water and in concentrated sulfuric acid and dyes cotton and fibers of regenerated cellulose by the after-coppering process in yellow shades of good fastness properties.

Similar dyestuifs are obtained when the dipyrazolone (XX) is coupled with the diazo compound from l-hydroxy-Z-aminobenzene-4-sulfonic acid methylamide or phenylamide or with the diazo compound from a mixture of these amides.

EXAMPLE 53 2 parts of the dyestufr described in Example 1, paragraphs 1 and 2, and 30 parts of sodium sulfate are dissolved in 3000 parts of water at 40-50". 100 parts of cotton are entered into the thus-prepared dyebath. The bath is heated to boiling in the course of a half hour and is retained at this temperature for a quarter hour, after which it is allowed to cool for a quarter hour. The dyed cotton is then withdrawn and rinsed well.

For after-coppering the dyed material is thoroughly manipulated for a half hour at 70 in a solution of 2 parts of crystalline copper sulfate, 2 parts of concentrated acetic acid and 3000 parts of water, and is then again rinsed and finaly dried. The metalliz'able dyestulr" of carb QXybenZene'A SiiIfOiiiE'a'cid mummies are replaced the other examples can be dyed in like manner.

EXAMPLE 54 2 parts of the copper complex compound, obtainable according to Example 5, paragraphs 1 to 3, are utilized for dyeing cotton in the manner described in the first paragraph of the preceding example. The thus-obtained dyeing has excellent fastness to light and to wet treatn The nbn-metalliz'abl'e dyestuffs as Well as the other hereinbefore' described metalliferou's dyestufl's can be dyed in like manner.

Having thus disclosed the invention, what is claimed is: selected from the group consisting of aminomonoazo and 1. A member selected from the group consisting of aminodisazo compounds. azo dyestufis which correspond to the formula v 2. The azo dyestulf WhlCh correspond to the formula COOH 50:11 801K 3. The azo dyestufl which corresponds to the formula H|C-C C-N=/N OH] I /COCuO(IJ SOaH nois- N=N NH-C 0-CH=CHC O-NH-QCH=CHO-N 808E SOIH 4. The azo dyestufi' which corresponds to the formula N =-Nil3CCHz BIC-BN-OJS- co-ouoo /N NQcH=oH-QNH-coc11= SOsH BOIH ..|2

5. The azo dyestuif which corresponds to the formula H0as :?-1 r=-N-c--c-0m o= o-bu-o-i ll l \N CH=0H NH-CO 01H SOIH flH $013 80111 (in I I I=N- 0-011.

SOz-NH-CH;

and the copper and nickel complex compounds thereof, 6. The azo dyestufi which corresponds to the formula wherein y stands for a member selected from the group N=N C 00H: consisting of hydroxy, methoxy and carboxy, one 2 stands 5 a LL.

for a member selected from the group consisting of hydrogen, chlorine, bromine and methyl, the other z stands so H l H (in for hydrogen, R stands for a member selected from the 70 H group consisting of radicals of the benzene series and of Nit-CO naphthalene sulfonic acid radicals, said radicals of the C N=N benzene series being free from sulfomc acid groups when 76 O OH I H y is carboxy, and A represents the radical of a member (R fer on folldwing page) 30 References Cited in the file of this patent 2,734,053 Grandjean et a1. Feb. 7, 1956 UNITED STATES PATENTS FOREIGN PATENTS 2,104,595 Schirm Jan. 4, 1938 2,646,338 Kappeler et a1. July 21, 1953 5 Belgmm My 1951 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,817,654 December 24, 1957 Philippe Grandjean et al.

It is herebi; certified that error appears in the printed specification of the above num ered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, line 61, for represent read -representative; column 8, line 48, for isazo read -disazo-; column 14, line 63, for sovled read -solved-; columns 23 and 24, in the table, third column thereof, opposite Example N o. 46, for napthalene read napl1tl1alene-; columns 25 and 26, Example 37, the right-hand portion of the formula should appear as shown below instead of as in the patent:

column 26, line 64, for finaly read -finally; column 28, line 3, for correspond read -corresponds.

Signed and sealed this 27th day of May 1958.

Attest: KARL H. AXLINE, Attestimg Oyficer.

ROBERT C. WATSON, Oomwnissz'oner of Patents. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF AZO DYESTUFFS WHICH CORRESPOND TO THE FORMULA 